[go: up one dir, main page]

US20100260931A1 - Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber - Google Patents

Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber Download PDF

Info

Publication number
US20100260931A1
US20100260931A1 US12/757,907 US75790710A US2010260931A1 US 20100260931 A1 US20100260931 A1 US 20100260931A1 US 75790710 A US75790710 A US 75790710A US 2010260931 A1 US2010260931 A1 US 2010260931A1
Authority
US
United States
Prior art keywords
cnt
substrate
catalyst
fiber
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/757,907
Other languages
English (en)
Inventor
Harry C. Malecki
Tushar K. Shah
Mark R. Alberding
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Applied Nanostructured Solutions LLC
Original Assignee
Lockheed Martin Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lockheed Martin Corp filed Critical Lockheed Martin Corp
Priority to US12/757,907 priority Critical patent/US20100260931A1/en
Assigned to APPLIED NANOSTRUCTURED SOLUTIONS, LLC reassignment APPLIED NANOSTRUCTURED SOLUTIONS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LOCKHEED MARTIN CORPORATION
Assigned to LOCKHEED MARTIN CORPORATION reassignment LOCKHEED MARTIN CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MALECKI, HARRY C., SHAH, TUSHAR K., ALBERDING, MARK R.
Publication of US20100260931A1 publication Critical patent/US20100260931A1/en
Assigned to APPLIED NANOSTRUCTURED SOLUTIONS, LLC reassignment APPLIED NANOSTRUCTURED SOLUTIONS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LOCKHEED MARTIN CORPORATION
Assigned to APPLIED NANOSTRUCTURED SOLUTIONS, LLC reassignment APPLIED NANOSTRUCTURED SOLUTIONS, LLC CORRECTIVE ASSIGNMENT TO CORRECT THE ERRONEOUSLY LISTED SERIAL NO. 12/757,901 PREVIOUSLY RECORDED ON REEL 025913 FRAME 0473. ASSIGNOR(S) HEREBY CONFIRMS THE SERIAL NO. 12/757,901 SHOULD BE REMOVED FROM THE ASSIGNMENT.. Assignors: LOCKHEED MARTIN CORPORATION
Abandoned legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/164—Preparation involving continuous processes

Definitions

  • the present invention relates in general to a system, method and apparatus for the continuous synthesis of carbon nanotubes.
  • Carbon nanotubes exhibit impressive physical properties such as exhibiting roughly eighty times the strength, six times the stiffness (i.e., Young's Modulus), and one-sixth the density of high carbon steel. CNTs can be useful when integrated into certain fibrous materials such as composite materials. Hence, developing CNTs within composite materials having these desirable properties is of significant interest.
  • a composite material is a heterogeneous combination of two or more constituents that differ in form or composition on a macroscopic scale.
  • Two constituents of a composite include a reinforcing agent and a resin matrix.
  • the fibers act as a reinforcing agent.
  • the resin matrix keeps the fibers in a desired location and orientation and also serves as a load-transfer medium between fibers within the composite. Due to their exceptional mechanical properties, CNTs are used to further reinforce the fiber in composite materials.
  • E-glass fibers can experience losses in strength of up to about 50%. These losses can propagate and cause further problems down the process line as deteriorated fibers can fray and break under tension and in low-radius turns. Other fibers including carbon fibers can experience similar problems. Alternative methods and systems for providing low temperature in-line CNT synthesis are desired.
  • a method for forming a CNT infused substrate comprises exposing a catalyst nanoparticle, a carbon feedstock gas, and a carrier gas to a CNT synthesis temperature, allowing a CNT to form on the catalyst nanoparticle, cooling the CNT, and exposing the cooled CNT to a surface of a substrate to form a CNT infused substrate.
  • the substrate can be functionalized prior to exposing the substrate to the CNT.
  • the CNT infused substrate can also be functionalized.
  • the method also comprises providing a catalyst solution comprising a catalyst and a solvent, and atomizing the catalyst solution and allowing the solvent to evaporate leaving the catalyst nanoparticle.
  • a system comprises a carrier gas source that provides a carrier gas; a catalyst source that provides a catalyst nanoparticle; a carbon feedstock source that provides a carbon feedstock; a substrate source that provides a substrate; and a CNT growth reactor comprising an inlet device that receives the carrier gas, the catalyst nanoparticle, and the carbon feedstock and introduces the carrier gas, the catalyst nanoparticle, and the carbon feedstock into a CNT growth zone; a heating element that heats the carrier gas, the catalyst nanoparticle, and the carbon feedstock to a CNT synthesis temperature within the CNT growth zone to allow a CNT to synthesize on the catalyst and form a synthesized CNT; a dispersion hood that receives the synthesized CNT and cools the synthesized CNT; and a CNT infusion chamber that receives the synthesized CNT and the substrate and exposes the substrate to the cooled synthesized CNT to produce a CNT infused substrate.
  • the substrate is functionalized.
  • a method comprises providing a catalyst nanoparticle, a carbon feedstock gas, and a carrier gas; heating the catalyst nanoparticle, the carbon feedstock gas, and the carrier gas to a CNT synthesis temperature; allowing a CNT to form on the catalyst nanoparticle; cooling the CNT; providing a substrate; exposing the substrate to the cooled CNT to form a CNT infused substrate; and forming a composite material, wherein the composite material comprises the CNT infused substrate.
  • the substrate is functionalized, and in some embodiments, the CNT infused substrate is functionalized prior to forming a composite material.
  • the substrate is provided on a dynamic basis.
  • FIG. 1 depicts a reactor configuration for the production of carbon nanotubes in accordance with some embodiments of the invention.
  • FIG. 2 depicts a method for providing a CNT infused substrate suitable for use in a composite material according to some embodiments of the invention.
  • the present invention relates in general to a system, method and apparatus for the continuous synthesis of CNTs and infusion on a substrate.
  • the invention provides at least some separation between the high-temperature synthesis of carbon nanotubes and their application to a substrate.
  • CNTs can be advantageously synthesized in a high temperature reactor and subsequently infused on a variety of substrates to produce carbon nanotube-infused (“CNT-infused”) substrates.
  • the process is particularly advantageous for use with temperature sensitive substrates or substrates with temperature sensitive sizings.
  • the disposition of CNTs on a substrate can serve many functions including, for example, as a sizing agent to protect against damage from moisture, oxidation, abrasion, and compression.
  • a CNT-based sizing can also serve as an interface between the substrate and a matrix material in a composite.
  • the CNTs can also serve as one of several sizing agents coating the substrate.
  • CNTs infused on a substrate can alter various properties of the substrate, such as thermal and/or electrical conductivity, and/or tensile strength, for example.
  • the processes employed to make CNT-infused substrates can provide CNTs with substantially uniform length and distribution to impart their useful properties uniformly over the substrate that is being modified. Furthermore, the processes disclosed herein can generate CNT-infused substrates of spoolable dimensions.
  • the system and method disclosed herein also make it possible to use various sizing and substrates such as polyaramid fibers including Kevlar, which cannot withstand high operating temperatures utilized in some conventional carbon nanotube synthesis processes.
  • the system and the method of this invention can allow a temperature sensitive substrate to be used for the formation of a composite material infused with CNTs due at least in part to the relatively low temperature at which the CNTs contact and are infused onto the substrate.
  • a further advantage of the present system and method is that continuous synthesis of CNTs can be obtained, facilitating mass production of composite materials with CNTs.
  • the continuous synthesis process can be carried out on a dynamic substrate, e.g., a substrate entering a reactor through an inlet, traversing through the reactor and exiting from an outlet of the reactor.
  • the processes described herein can allow for the continuous production of CNTs of uniform length and distribution along spoolable lengths of tow, tapes, fabrics and other 3D woven structures. While various mats, woven and non-woven fabrics and the like can be functionalized by processes of the invention, it is also possible to generate such higher ordered structures from the parent tow, yarn or the like after CNT functionalization of these parent materials. For example, a CNT-infused woven fabric can be generated from a CNT-infused fiber tow.
  • substrate is intended to include any material upon which CNTs can be synthesized and can include, but is not limited to, a carbon fiber, a graphite fiber, a cellulosic fiber, a glass fiber, a metal fiber (e.g., steel, aluminum, etc.), a ceramic fiber, a metallic-ceramic fiber, cellulosic fiber, an aramid fiber (e.g., Kevlar), thermoplastics, or any substrate comprising a combination thereof.
  • the substrate can include fibers or filaments arranged, for example, in a fiber tow (typically having about 1000 to about 12000 fibers) as well as planar substrates such as fabrics, tapes, ribbons, graphene sheets, silicon wafers, or other fiber broadgoods, and materials upon which CNTs can be synthesized.
  • a fiber tow typically having about 1000 to about 12000 fibers
  • planar substrates such as fabrics, tapes, ribbons, graphene sheets, silicon wafers, or other fiber broadgoods, and materials upon which CNTs can be synthesized.
  • spoolable dimensions refers to substrates having at least one dimension that is not limited in length, allowing for the material to be stored on a spool or mandrel. Substrates of “spoolable dimensions” have at least one dimension that indicates the use of either batch or continuous processing for CNT infusion as described herein.
  • Commercial carbon fiber tow in particular, can be obtained in 5, 10, 20, 50, and 100 lb. (for spools having high weight, usually a 3 k/12K tow) spools, for example, although larger spools may require special order.
  • CNT carbon nanotube
  • SWNT single-walled CNTs
  • DWNT double-walled CNTs
  • MWNTs multi-walled CNTs
  • uniform in length refers to length of CNTs grown in a reactor. “Uniform length” means that the CNTs have lengths with tolerances of plus or minus about 20% of the total CNT length or less, for CNT lengths varying from between about 1 micron to about 500 microns. At very short lengths, such as 1-4 microns, this error can be in a range from between about plus or minus 20% of the total CNT length up to about plus or minus 1 micron, that is, somewhat more than about 20% of the total CNT length.
  • uniform in distribution refers to the consistency of density of CNTs on a substrate. “Uniform distribution” means that the CNTs have a density on the substrate with tolerances of plus or minus about 10% coverage defined as the percentage of the surface area of the substrate covered by CNTs. This is equivalent to ⁇ 1500 CNTs/ ⁇ m 2 for an 8 nm diameter CNT with 5 walls. Such a value assumes the space inside the CNTs as fillable.
  • the term “infused” means bonded and “infusion” means the process of bonding. Such bonding can involve direct covalent bonding, ionic bonding, pi-pi, and/or Van der Waals force-mediated physisorption.
  • the CNTs can be directly bonded (e.g., covalently or through a pi-pi bond) to the substrate, for example, at a point at which the substrate has been functionalized. Bonding can be indirect, such as the CNT infusion to the substrate via a coating disposed between the CNTs and substrate.
  • the CNTs can be indirectly bonded (e.g., through physisorption) to the substrate without any intervening materials and/or functionalization.
  • the CNTs can be “infused” to the substrate directly or indirectly. The particular manner in which a CNT is “infused” to a substrates can be referred to as a “bonding motif.”
  • transition metal refers to any element or alloy of elements in the d-block of the periodic table.
  • the tetin “transition metal” also includes salt forms of the base transition metal element such as oxides, carbides, chlorides, chlorates, acetates, sulfides, sulfates, nitrides, nitrates and the like.
  • nanoparticle or NP (plural NPs), or grammatical equivalents thereof refers to particles sized between about 0.1 to about 100 nanometers in equivalent spherical diameter, although the NPs need not be spherical in shape. Transition metal NPs, in particular, serve as catalysts for CNT synthesis within the reactor.
  • carbon feedstock refers to any carbon compound gas, solid, or liquid that can be volatilized, nebulized, atomized, or otherwise fluidized and is capable of dissociating or cracking at high temperatures into at least some free carbon radicals and which, in the presence of a catalyst, can form CNTs.
  • free carbon radicals refers to any reactive carbon species capable of adding to the growth of a CNT. Without intending to be limited by theory, it is believed that a free carbon radical adds to the growth of a CNT by associating with a CNT catalyst to form a CNT or increase the length of an existing CNT.
  • sizing agent refers collectively to materials used in the manufacture of some substrates (e.g., carbon fibers) as a coating to protect the integrity of substrate, provide enhanced interfacial interactions between a substrate and a matrix material in a composite, and/or alter and/or enhance particular physical properties of a substrate.
  • CNTs infused to substrates can behave as a sizing agent.
  • the term “material residence time” refers to the amount of time a discrete point along a substrate of spoolable dimensions is exposed to synthesized CNTs within the reactor during the CNT infusion processes described herein. This definition includes the residence time when employing multiple CNT growth chambers.
  • linespeed refers to the speed at which a substrate of spoolable dimensions can be fed through the CNT infusion processes described herein, where linespeed is a velocity determined by dividing CNT chamber(s) length by the material residence time.
  • FIG. 1 there is illustrated a schematic diagram of a reactor 100 for synthesis of a CNT infused substrate.
  • catalyst source 104 carbon feedstock source 106 , and carrier gas source 102 are introduced at the top of the CNT growth zone 112 through an inlet device 108 .
  • a heating element 110 can be used to raise the temperature of the mixture to promote the formation of CNTs.
  • the synthesized CNTs can infuse to substrate 118 to produce a CNT infused substrate before passing out of the reactor 100 for further processing.
  • catalyst source 104 provides a catalyst for initiating the synthesis of CNTs.
  • a catalyst can take the form of nano-sized particles of a catalyst.
  • the catalyst employed can be a transition metal nanoparticle which can be any d-block transition metal as described above.
  • the nanoparticles (NPs) can include alloys and non-alloy mixtures of d-block metals in elemental form or in salt form, and any mixtures thereof.
  • Such salt forms include, without limitation, oxides, carbides, chlorides, chlorates, acetates, sulfides, sulfates, nitrides, nitrates and mixtures thereof.
  • Non-limiting exemplary transition metal NPs include Ni, Fe, Co, Mo, Cu, Pt, Au, and Ag and salts thereof. Many of these transition metal catalysts are commercially available from a variety of suppliers, including, for example, Ferrotec Corporation (Bedford, N.H.).
  • the catalyst can be in a colloidal solution or a metal salt solution.
  • Other catalyst solutions can also be used.
  • commercial dispersions of CNT-forming transition metal nanoparticle catalyst are available and are used without dilution.
  • commercial dispersions of catalyst can be diluted. Whether to dilute such solutions can depend on the conditions within the reactor and the relative flow rates of the catalyst, the carrier gas, and the carbon feedstock.
  • Catalyst solutions can comprise a solvent that allows the catalyst to be uniformly dispersed throughout the catalyst solution.
  • Such solvents can include, without limitation, water, acetone, hexane, isopropyl alcohol, toluene, ethanol, methanol, tetrahydrofuran (THF), cyclohexane or any other solvent with controlled polarity to create an appropriate dispersion of the CNT-forming catalyst nanoparticles or salt solutions.
  • Concentrations of CNT-forming catalyst can be in a range from about 1:1 to about 1:10000 of catalyst to solvent in the catalyst solution.
  • carbon feedstock source 106 is in fluid communication with the top of the CNT growth zone 112 through an inlet device 108 .
  • gases from carbon feedstock source 106 and carrier gas source 102 are mixed before the gas mixture is supplied to the CNT growth zone 112 through an inlet device 108 .
  • the carbon feedstock can be any carbon compound gas, solid, or liquid that can be volatilized, nebulized, atomized, or otherwise fluidized and is capable of dissociating or cracking at high temperatures into at least some free carbon radicals.
  • the free carbon radicals can then form CNTs in the presence of a catalyst.
  • the carbon feedstock can comprise acetylene, ethylene, methanol, methane, propane, benzene, natural gas, or any combination thereof.
  • a carbon feedstock comprising acetylene is heated to a temperature between about 450° C. and about 1000° C.
  • CNT growth zone 112 At least a portion of the acetylene dissociates into carbon and hydrogen in the presence of a catalyst nanoparticle.
  • the temperature of the CNT growth zone facilitates rapid dissociation of acetylene but could adversely impact the physical and chemical properties of the substrate and/or any sizing materials present.
  • the use of a carbon feedstock such as acetylene can reduce the need for a separate process of introducing hydrogen into CNT growth zone 112 , which can be used to reduce a catalyst containing an oxide.
  • the dissociation of a carbon feedstock may provide hydrogen, which can reduce the catalyst particles to pure particles (e.g., in a pure elemental form) or at least to an acceptable oxide level.
  • the stability of an oxide used as a catalyst can affect the reactivity of the catalyst particles. As the stability of the oxide increases, the catalyst particles generally become less reactive. Reduction (e.g., through contact with hydrogen) to a more unstable oxide or a pure metal can increase the reactivity of the catalyst.
  • the catalyst comprises iron oxide (e.g., magnetite)
  • iron oxide e.g., magnetite
  • such an iron oxide particle is not conducive to the synthesis of CNTs due to the stability of the iron oxide. Reduction to a less stable oxidation state or pure iron can increase the reactivity of the catalyst particle.
  • the hydrogen from acetylene can remove the oxide from the catalyst particles or reduce the oxide to a less stable oxide form.
  • a carrier gas can be used to control the bulk flow of catalyst and carbon feedstock through the CNT growth zone 112 in addition to removing oxygen, which can be detrimental to the growth of CNTs from CNT growth zone 112 . If oxygen is present in CNT growth zone 112 , the carbon radicals formed from the carbon feedstock tend to react with the oxygen to form carbon dioxide and/or carbon monoxide, instead of forming CNTs using the catalyst nanoparticles as seed structures. In addition, the formation of a CNT in the presence of oxygen can result in the oxidative decomposition of the CNT.
  • the carrier gas can comprise any inert gas that does not detrimentally impact the CNT growth process.
  • the carrier gas can include, but is not limited to, nitrogen, helium, argon, or any combination thereof.
  • the carrier gas can comprise a gas that allows for control of the process parameters.
  • a gas can include, but is not limited to, water vapor and/or hydrogen.
  • the carbon feedstock can be provided in a range between about 0% to about 15% of the total gas mixture.
  • the catalyst from catalyst source 104 , the gases from carbon feedstock source 106 , and the gases from carrier gas source 102 can be supplied to the CNT growth zone 112 through an inlet device 108 .
  • the inlet device can comprise one or more devices for introducing the gases and the catalyst together or separately.
  • inlet device 108 comprises an atomizer and the catalyst is introduced to the reactor as a catalyst solution in an atomized form. This can be achieved via a nebulizer, atomization nozzle, or other techniques.
  • Industrial atomizer or misting nozzle designs can be based on the use of high pressure fluid (e.g., a liquid) or a gas assist nozzle design.
  • the catalyst solution pressure can be used to accelerate the fluid through small orifices and create shear forces inside nozzle passages that break down the catalyst solution into micron size droplets.
  • the shear energy is supplied by the catalyst solution, which can be at high-pressure.
  • the inertial force created by supersonic gas jets e.g., the carbon feedstock, carrier gas, or a combination of the two shears the catalyst solution while inside the atomizer nozzle and upon exiting the atomizer nozzle, breaks the catalyst solution into micron size droplets.
  • the catalyst solution is passed through a nebulizer to produce the catalyst solution in an atomized form.
  • a nebulizer may operate through the introduction of a high pressure gas (e.g., the carbon feedstock, the carrier gas, or a combination of the two) through a reservoir containing the catalyst solution. The action of the gas passing through the solution can entrain a portion of the catalyst solution to produce an atomized carrier solution. Alternatively, a membrane oscillating at a high frequency and in contact with the carrier solution can be used to produce an atomized catalyst solution. A gas can then pass over the atomized catalyst solution to carry the atomized catalyst solution through inlet device 108 into the CNT growth zone 112 .
  • a high pressure gas e.g., the carbon feedstock, the carrier gas, or a combination of the two
  • the gas can comprise the carrier gas, the carbon feedstock, or any mixture thereof.
  • a high-pressure liquid nozzle is used to atomize the catalyst solution and the carrier gas and the carbon feedstock are introduced through inlet device 108 separate from the catalyst solution, either individually or as a combined gas mixture. As the catalyst solution passes through inlet device 108 , the catalyst solution can vaporize and leave a catalyst nanoparticle.
  • the catalyst can be in a colloidal solution so that the fluid portion of the solution vaporizes leaving a catalyst nanoparticle, or the catalyst can be a salt dissolved in a solvent so that the evaporation of the solvent results in the crystallization of a catalyst nanoparticle.
  • heating element 110 can be used to raise the temperature of the components entering the CNT growth zone 112 to promote the formation of CNTs.
  • the heating element can comprise any type of heating element capable of raising the temperature of the CNT growth zone, the catalyst nanoparticles, the carbon feedstock, or any combination thereof to the appropriate reaction temperature.
  • heating element 110 can comprise a plurality of individual heating elements capable of producing a desired temperature and/or a desired temperature profile within the CNT growth zone.
  • heating element 110 can include, but is not limited to, infrared or resistive heaters disposed adjacent to or within the growth zone.
  • Heating element 110 heats the catalyst and gases to a CNT synthesis temperature, which is typically in the range of about 450° C. to about 1000° C. At these temperatures, at least a portion of the carbon feedstock can dissociate or crack into at least some free carbon radicals. The catalyst nanoparticles can then react with the free carbon radicals to synthesize CNTs. In some embodiments, hydrogen is also produced by the dissociation of the carbon feedstock, which can then reduce the catalyst to a pure metal particle.
  • the synthesized CNTs can comprise agglomerates of synthesized CNTs and one or more catalyst particles.
  • the length of the CNTs is affected by several factors including, but not limited to, the carbon feedstock concentration, the temperature, the catalyst composition, the carrier gas flowrate, and the residence time of the catalyst particles and synthesizing CNTs in the CNT growth zone, which may be a function of the length of the CNT growth zone and the gas flow characteristics (e.g., velocity, etc.).
  • heating element 110 and/or CNT growth zone 112 can be constructed of metal, (e.g., stainless steel, a high nickel steel alloy, etc.). This use of metal, and stainless steel in particular, can lead to carbon deposition (i.e., soot and by-product formation). Once carbon deposits to a monolayer on the walls of the device, carbon will readily deposit over itself.
  • the metal can be coated to prevent or reduce carbon deposits. Suitable coating can include, but are not limited to, silica, alumina, magnesium oxide, and any combination thereof. When carbon deposits occur, periodic cleaning and maintenance can be employed to prevent any carbon deposition from obstructing the flow of the gases, the catalyst particles, the CNTs, or any combination thereof.
  • the CNTs pass to a dispersion hood 114 after passing out of the CNT growth zone 112 where the synthesized CNTs can cool prior to entering the infusion chamber 116 containing a substrate 118 .
  • the dispersion hood 114 can provide a buffer region where the gas mixture (e.g., any remaining carbon feedstock gas, dissociation products, and/or carrier gas) and synthesized CNTs can be cooled before reaching the substrate.
  • the dispersion hood can comprise one or more cooling devices such as a heat transfer arrangement for cooling the outside of the dispersion hood or otherwise removing heat from the gas mixture containing the synthesized CNTs.
  • the dispersion hood is designed so that the temperature of the synthesized CNTs is lowered to a temperature ranging from about 25° C. to about 450° C.
  • the substrate is not exposed to the high temperatures that are required for CNT synthesis.
  • the degradation of the substrate and/or removal of the sizing that would otherwise compromise the substrate properties can be avoided.
  • the synthesized CNTs can infuse to substrate 118 to produce a CNT infused substrate before passing out of the reactor 100 for further processing.
  • the substrate can include any of those materials listed above as being suitable for use as a substrate.
  • the substrate can comprise E-glass fibers coated with a sizing material.
  • the substrate can include other fibers, such as inexpensive glass fibers and carbon fibers.
  • the substrate can be an aramid fiber such as Kevlar. Fibers can be supplied in bundles, known as “tows.” A tow can have between about 1000 to about 12000 fiber filaments.
  • a fiber filament can have a diameter of about 10 microns, although fiber filaments having other diameters can be used.
  • Fibers can also include a carbon yarn, a carbon tape, a unidirectional carbon tape, a carbon fiber-braid, a woven carbon fabric, a non-woven carbon fiber mat, a carbon fiber ply, a 3D woven structure and the like.
  • the substrate can be coated with a sizing.
  • Sizing can vary widely in type and function and can include, but is not limited to, surfactants, anti-static agents, lubricants, siloxanes, alkoxysilanes, aminosilanes, silanes, silanols, polyvinyl alcohol, starch, and mixtures thereof.
  • Such sizing can be used to protect the CNTs themselves or provide further properties to the fiber not imparted by the presence of the infused CNTs.
  • any sizing can be removed prior to the substrate entering reactor 100 .
  • a coating such as silica, alumina, magnesium oxide, silane, siloxane, or other type coating can be coated on the substrate to aid in bonding the CNTs to the substrate. Without intending to be limited by theory, it is believed that the bonding of the CNTs to the substrate with this type of coating is more mechanical and depends on physisorption and/or mechanical interlocking.
  • the substrate can be functionalized to promote the infusion of the synthesized CNTs to the substrate.
  • Functionalization generally involves the creation of polar functional groups on the surface of the substrate. Suitable functional groups can include, but are not limited to, amine groups, carbonyl groups, carboxyl groups, fluorine-based groups, silane groups, siloxane groups, and any combination thereof.
  • the polar groups can take place in the infusion of the synthesized CNTs to the substrate through the interaction of the polar group and the carbon atoms in the CNTs.
  • the substrate can be functionalized using any technique known to one of ordinary skill in the art. Suitable techniques can include, but are not limited to, sputtering, plasma functionalization, and passing the substrate through one or more suitable chemical solutions.
  • the CNTs can infuse to substrate 118 to produce a CNT infused substrate before passing out of the reactor 100 for further processing.
  • substrate 118 can be supplied to reactor on a dynamic basis.
  • the synthesized CNTs can comprise one or more carbon radicals (e.g., dangling carbons) due to disorder along the CNT walls or carbon radicals at an end of the CNT that are not capped during the CNT synthesis process.
  • these radicals can form a bond with a functionalized substrate.
  • the resulting infused substrate may have the synthesized CNTs bonded at their ends to the substrate surface, creating a comb like pattern on the substrate surface.
  • the radicals can be present along the walls of the CNTs and can bond to a substrate at these points along the walls.
  • the synthesized CNTs may be infused to the surface of a substrate based on associative forces that are weaker than covalent bonds. Thus, a variety of bonding motifs are also possible, which can result in a variety of CNT infused substrate structures.
  • the resulting infused substrate can then pass out of reactor 100 for further processing.
  • the CNT-infused substrates can include a substrate such as a carbon filament, a carbon fiber yarn, a carbon fiber tow, a carbon tape, a carbon fiber-braid, a woven carbon fabric, a non-woven carbon fiber mat, a carbon fiber ply, and other 3D woven structures.
  • Filaments include high aspect ratio fibers having diameters ranging in size from between about 1 micron to about 100 microns. Fiber tows are generally compactly associated bundles of filaments and are usually twisted together to give yarns
  • controllers can form a controller system that can be adapted to independently sense, monitor and control system parameters including one or more of substrate feed rate, the carrier gas flow rate and pressure, the catalyst flowrate and pressure, the carbon feedstock flowrate and pressure, the heating element, and the temperature within the CNT growth zone.
  • a controller system can be an integrated, automated computerized system controller system that receives parameter data and performs various automated adjustments of control parameters or a manual control arrangement, as is understood by one of ordinary skill in the art.
  • a post functionalization process for functionalizing the carbon nanotubes can be performed to promote adhesion of the carbon nanotubes to a resin matrix.
  • Functionalization generally involves the creation of polar functional groups on the surface of the CNT.
  • Suitable functional groups for can include, but are not limited to, amine groups, carbonyl groups, carboxyl groups, fluorine-based groups, silane groups, siloxane groups, and any combination thereof.
  • Suitable techniques can include, but are not limited to, sputtering, plasma functionalization, and passing the substrate through one or more suitable chemical solutions.
  • FIG. 1 illustrates a generally vertical reactor design
  • the reactor system is not limited to the design shown in FIG. 1 .
  • the reactor including the CNT growth zone, can be oriented in a non-vertical arrangement.
  • the flow of gases through the CNT growth zone can generally entrain the catalyst particles and any synthesized CNTs along with the bulk gas flow.
  • the catalyst particles may pass through a CNT growth zone in a generally horizontal direction before passing to a dispersion hood outside the CNT growth zone.
  • the orientation of the reactor can vary.
  • FIG. 2 illustrates a flow chart of a method for synthesizing CNTs.
  • an atomized catalyst solution is provided in step 202 along with a carbon feedstock gas in step 204 and carrier gas in step 206 .
  • the catalyst solution, the carbon feedstock, and/or the carrier gas are combined prior to atomization and heating of the solution.
  • the catalyst solution, the carbon feedstock gas, and the carrier gas are then heated to CNT synthesis temperatures in step 208 .
  • the CNT synthesis temperature can range from about 450° C. to about 1000° C.
  • the mixture is maintained in a CNT growth zone at the CNT synthesis temperatures for an amount of time sufficient to synthesize CNTs of a desired length and size.
  • the synthesized CNTs then pass along with the carrier gas and are cooled in step 210 .
  • the mixture may pass through a device such as a dispersion hood to cool to a temperature ranging from about 25° C. to about 450° C.
  • the cooling can avoid the degradation of a temperature sensitive substrate and/or the removal of the sizing that can otherwise compromise the substrate properties.
  • the synthesized CNTs can then be exposed to a substrate.
  • a substrate can be optionally functionalized at step 211 before being exposed to the synthesized CNTs.
  • the substrate can be exposed to the synthesized CNTs that pass through the cooling zone in step 212 .
  • the substrate can be introduced on a dynamic basis.
  • the synthesized CNTs can bond with the substrate to produce a CNT infused substrate.
  • the CNT infused substrate can then pass out of the reactor for further use or processing.
  • the CNT infused substrate can be optionally functionalized to improve the adhesion of the CNT infused substrate with a resin matrix.
  • FIG. 3 depicts an E-Glass fiber with CNTs infused on its surface via a vertical furnace growth chamber in accordance with some embodiments of the invention.
  • Higher density and shorter CNTs can be useful for improving mechanical properties, while longer CNTs with lower density are useful for improving thermal and electrical properties, although increased density is still favorable.
  • a lower density can result when longer CNTs are grown. This can be the result of the higher temperatures and more rapid growth causing lower catalyst particle yields.
  • the CNT infused substrate can be used to form a composite material.
  • Such composite materials can comprise a matrix material to form a composite with the CNT-infused substrate.
  • Matrix materials useful in the present invention can include, but are not limited to, resins (polymers), both thermosetting and thermoplastic, metals, ceramics, and cements.
  • Thermosetting resins useful as matrix materials include phthalic/maelic type polyesters, vinyl esters, epoxies, phenolics, cyanates, bismaleimides, and nadic end-capped polyimides (e.g., PMR-15).
  • Thermoplastic resins include polysulfones, polyamides, polycarbonates, polyphenylene oxides, polysulfides, polyether ether ketones, polyether sulfones, polyamide-imides, polyetherimides, polyimides, polyarylates, and liquid crystalline polyester.
  • Metals useful as matrix materials include alloys of aluminum such as aluminum 6061, 2024, and 713 aluminum braze. Ceramics useful as matrix materials include carbon ceramics, such as lithium aluminosilicate, oxides such as alumina and mullite, nitrides such as silicon nitride, and carbides such as silicon carbide.
  • Cements useful as matrix materials include carbide-base cermets (tungsten carbide, chromium carbide, and titanium carbide), refractory cements (tungsten-thoria and barium-carbonate-nickel), chromium-alumina, nickel-magnesia iron-zirconium carbide. Any of the above-described matrix materials can be used alone or in combination.
  • This prophetic example shows how a carbon fiber material can be infused with CNTs in a continuous process utilizing an embodiment of the vertical furnace.
  • FIG. 1 depicts system 100 for producing CNT-infused fiber in accordance with the illustrative embodiment of the present invention.
  • System 100 includes a catalyst source 104 , carbon feedstock source 106 , and carrier gas source 102 , CNT growth zone 112 , gas/vapor inlet device 108 , a heating element 110 , a dispersion hood 114 , an infusion chamber 116 , a plasma system (not illustrated), and a carbon fiber substrate 118 .
  • Carrier gas source 102 provides a flow of nitrogen gas at a rate of about 60 liters/minute, which mixes with acetylene gas from the carbon feedstock source 106 supplied at a rate of about 1.2 liters/minute.
  • the nitrogen/acetylene gas mixture is used as the atomizing gas in a nebulizer spray system, gas/vapor inlet device 108 , where a 1% mass iron acetate solution in isopropyl alcohol is used as the catalyst source 104 .
  • the atomized catalyst/carrier/feedstock gas mixture is introduced to an about 2.5 cm diameter, 92 cm long CNT growth zone 112 .
  • CNT growth zone 112 is heated by two independently controlled heating elements 110 .
  • the heating elements are stacked one on top of the other, each of a length of about 46 cm long.
  • the first heating element is used to preheat the gas/vapor mixture to CNT growth temperatures.
  • the second heating element is used to maintain growth temperature for the necessary growth residence time for the proper length CNT.
  • the gas/vapor residence time is about 30 seconds which allows for a uniform CNT length of about 20 microns.
  • Vapor phase CNTs are gravity assisted to dispersion hood 114 where the size of the zone increases from about 2.5 cm to an about 2.5 ⁇ 7.5 cm rectangular cross section.
  • the dispersion hood spreads out falling vapor phase CNTs for a more uniform application to fibers passing by beneath the hood in CNT infusion chamber 116 .
  • Carbon fiber substrate 118 is exposed to a plasma system where controlled oxygen treatment is used to functionalize the fiber surface.
  • An argon based plasma is used with a mixture of about 1% oxygen by volume to apply carbonyl and carboxyl functional groups on the surface of carbon fiber substrate 118 .
  • Functionalized carbon fiber substrate 118 is pulled through CNT infusion chamber 116 where vapor phase CNTs pass through dispersion hood 114 and applied to the carbon fiber surface.
  • Carbonyl and carboxyl functional groups act as infusion points for CNTs, where dangling carbon bonds at the CNT ends or at disorder on the CNT walls provide the bonding point.
  • Fibers are pulled through the infusion chamber at a linespeed of about 150 cm/minute. By varying the linespeed, the density of CNT infusion can be controlled. At the rate described in this example, a density of between about 2000 to about 4000 CNT/ ⁇ m 2 is achieved.
  • CNT infused carbon fiber passes out of CNT infusion chamber 116 and is wound on a spool for packaging and storage. Additional functionalization steps can occur after the CNT infusion process to enhance future CNT to matrix interfacial properties, but this is beyond the scope of this example.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
US12/757,907 2009-04-10 2010-04-09 Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber Abandoned US20100260931A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/757,907 US20100260931A1 (en) 2009-04-10 2010-04-09 Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16852609P 2009-04-10 2009-04-10
US12/757,907 US20100260931A1 (en) 2009-04-10 2010-04-09 Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber

Publications (1)

Publication Number Publication Date
US20100260931A1 true US20100260931A1 (en) 2010-10-14

Family

ID=42934602

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/757,907 Abandoned US20100260931A1 (en) 2009-04-10 2010-04-09 Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber

Country Status (10)

Country Link
US (1) US20100260931A1 (fr)
EP (1) EP2417288A4 (fr)
JP (1) JP5604506B2 (fr)
KR (1) KR20120002980A (fr)
CN (1) CN102388172B (fr)
AU (1) AU2010233113A1 (fr)
BR (1) BRPI1014162A2 (fr)
CA (1) CA2757474A1 (fr)
WO (1) WO2010118381A1 (fr)
ZA (1) ZA201106734B (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8580342B2 (en) 2009-02-27 2013-11-12 Applied Nanostructured Solutions, Llc Low temperature CNT growth using gas-preheat method
US20140186547A1 (en) * 2012-12-29 2014-07-03 Hon Hai Precision Industry Co., Ltd. Reactor and method for growing carbon nanotube using the same
US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US9260646B2 (en) 2012-05-09 2016-02-16 Laird Technologies, Inc. Polymer matrices functionalized with carbon-containing species for enhanced thermal conductivity
WO2016087857A1 (fr) * 2014-12-05 2016-06-09 Q-Flo Limited Procédé
CN105908491A (zh) * 2016-05-31 2016-08-31 哈尔滨工业大学 制备表面生长有碳纳米管的连续碳纤维的装置和方法
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
WO2018034625A1 (fr) * 2016-08-16 2018-02-22 Istanbul Teknik Universitesi Nanotubes de carbone à répartition aléatoire et/ou croissance verticale/horizontale sur des nanofibres polymères et leurs composites
US9987608B2 (en) 2014-09-19 2018-06-05 NanoSynthesis Plus, Ltd. Methods and apparatuses for producing dispersed nanostructures
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
WO2020071655A1 (fr) * 2018-10-04 2020-04-09 Awexomeray Procédé de préparation d'un fil comprenant des nanotubes de carbone et fil ainsi préparé
US10643816B1 (en) 2019-04-04 2020-05-05 aweXomeRay Co., Ltd. X-ray emitting device comprising a focusing electrode composed of a ceramic-based material
US20210187788A1 (en) * 2018-05-31 2021-06-24 Lintec Corporation Method of producing carbon-resin composite material, and composite structure for producing carbon-resin composite material
US11195684B2 (en) 2019-07-26 2021-12-07 Awexome Ray, Inc. Field emission apparatus with superior structural stability and X-ray tube comprising the same
EP3810547A4 (fr) * 2018-06-22 2022-04-06 The Government of the United States of America, as represented by the Secretary of the Navy Appareil et procédé de croissance de structures de carbone sp2 cylindriques ultralongues distinctes
US11453591B2 (en) 2018-11-30 2022-09-27 Awexome Ray, Inc. Process for preparing a carbon nanotube sheet comprising a uniaxially aligned yarn and carbon nanotube sheet prepared thereby
US11600462B2 (en) 2019-01-24 2023-03-07 Awexome Ray, Inc. Emitter with excellent structural stability and enhanced efficiency of electron emission and X-ray tube comprising the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106395791A (zh) * 2016-08-26 2017-02-15 宁波埃飞化工科技有限公司 一种碳纳米管的喷雾式窑炉及其生产方法
CN112974010A (zh) * 2019-12-13 2021-06-18 南京源昌新材料有限公司 一种用于碳纳米管原料雾化的专用雾化装置
CN116060279B (zh) * 2022-12-15 2024-06-07 深圳稀光新材料有限公司 油性油墨喷涂方法

Citations (97)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304855A (en) * 1963-05-15 1967-02-21 H G Molenaar & Company Proprie Extractor means for extracting liquid from a liquids containing mass
US4566969A (en) * 1981-09-29 1986-01-28 Crane & Co., Inc. Rolling filter apparatus
US4797378A (en) * 1986-02-18 1989-01-10 Minnesota Mining And Manufacturing Company Internally modified ceramic fiber
US5093155A (en) * 1988-11-29 1992-03-03 Tonen Corporation Process for sizing reinforcing fiber by applying sulfone compounds containing sulfonyl groups and sized reinforcing fibers obtained thereby
US5595750A (en) * 1991-08-09 1997-01-21 E. I. Du Pont De Nemours And Company Antimicrobial particles of silver and barium sulfate or zinc oxide
US5714089A (en) * 1984-10-31 1998-02-03 Igen International, Inc. Luminescent metal chelatte labels and means for detection
US6184280B1 (en) * 1995-10-23 2001-02-06 Mitsubishi Materials Corporation Electrically conductive polymer composition
US6221154B1 (en) * 1999-02-18 2001-04-24 City University Of Hong Kong Method for growing beta-silicon carbide nanorods, and preparation of patterned field-emitters by chemical vapor depositon (CVD)
US20020035170A1 (en) * 1999-02-12 2002-03-21 Paul Glatkowski Electromagnetic shielding composite comprising nanotubes
US6361861B2 (en) * 1999-06-14 2002-03-26 Battelle Memorial Institute Carbon nanotubes on a substrate
US20030024884A1 (en) * 2001-04-02 2003-02-06 Petrik Viktor Ivanovich Method for removing oil, petroleum products and/or chemical, pollutants from liquid and/or gas and/or surface
US6528572B1 (en) * 2001-09-14 2003-03-04 General Electric Company Conductive polymer compositions and methods of manufacture thereof
US20030068432A1 (en) * 1998-08-14 2003-04-10 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube devices
US6673392B2 (en) * 2000-03-15 2004-01-06 Samsung Sdi Co., Ltd. Method of vertically aligning carbon nanotubes on substrates at low pressure using thermal chemical vapor deposition with DC bias
US20040007955A1 (en) * 2002-07-09 2004-01-15 Zvi Yaniv Nanotriode utilizing carbon nanotubes and fibers
US20040009115A1 (en) * 2002-06-13 2004-01-15 Wee Thye Shen Andrew Selective area growth of aligned carbon nanotubes on a modified catalytic surface
US20040026234A1 (en) * 2000-08-23 2004-02-12 Pierre Vanden Brande Method and device for continuous cold plasma deposition of metal coatings
US6692717B1 (en) * 1999-09-17 2004-02-17 William Marsh Rice University Catalytic growth of single-wall carbon nanotubes from metal particles
US20040037767A1 (en) * 2002-08-21 2004-02-26 First Nano, Inc. Method and apparatus of carbon nanotube fabrication
US20040079278A1 (en) * 2002-10-28 2004-04-29 Kamins Theodore I. Method of forming three-dimensional nanocrystal array
US20040082247A1 (en) * 2002-03-21 2004-04-29 Shahyaan Desai Fibrous micro-composite material
US6837928B1 (en) * 2001-08-30 2005-01-04 The Board Of Trustees Of The Leland Stanford Junior University Electric field orientation of carbon nanotubes
US20050009694A1 (en) * 2003-06-30 2005-01-13 Watts Daniel J. Catalysts and methods for making same
US20050026778A1 (en) * 2002-02-25 2005-02-03 Axtell Holly C. Multi-functional protective fiber and methods for use
US6852410B2 (en) * 2002-07-01 2005-02-08 Georgia Tech Research Corporation Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same
US6863942B2 (en) * 1998-06-19 2005-03-08 The Research Foundation Of State University Of New York Free-standing and aligned carbon nanotubes and synthesis thereof
US20050090176A1 (en) * 2001-08-29 2005-04-28 Dean Kenneth A. Field emission display and methods of forming a field emission display
US20060002844A1 (en) * 2004-07-02 2006-01-05 Kabushiki Kaisha Toshiba Manufacturing methods of catalysts for carbon fiber composition and carbon material compound, manufacturing methods of carbon fiber and catalyst material for fuel cell, and catalyst material for fuel cell
US6986877B2 (en) * 2002-01-08 2006-01-17 Futaba Corporation Method for preparing nano-carbon fiber and nano-carbon fiber
US6986853B2 (en) * 2001-03-26 2006-01-17 Eikos, Inc. Carbon nanotube fiber-reinforced composite structures for EM and lightning strike protection
US6994907B2 (en) * 1999-06-02 2006-02-07 The Board Of Regents Of The University Of Oklahoma Carbon nanotube product comprising single-walled carbon nanotubes
US20060052509A1 (en) * 2002-11-01 2006-03-09 Mitsubishi Rayon Co., Ltd. Composition containing carbon nanotubes having coating thereof and process for producing them
US7011760B2 (en) * 2001-12-21 2006-03-14 Battelle Memorial Institute Carbon nanotube-containing structures, methods of making, and processes using same
US20060062944A1 (en) * 2004-09-20 2006-03-23 Gardner Slade H Ballistic fabrics with improved antiballistic properties
US7018600B2 (en) * 2001-03-21 2006-03-28 Gsi Creos Corporation Expanded carbon fiber product and composite using the same
US20060067871A1 (en) * 2004-05-26 2006-03-30 Massachusetts Institute Of Technology Methods and devices for growth and/or assembly of nanostructures
US7022776B2 (en) * 2001-11-07 2006-04-04 General Electric Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom
US20060083927A1 (en) * 2004-10-15 2006-04-20 Zyvex Corporation Thermal interface incorporating nanotubes
US20060083674A1 (en) * 2003-02-14 2006-04-20 Shigeo Maruyama Method for forming catalyst metal particles for production of single-walled carbon nanotube
US7157068B2 (en) * 2001-05-21 2007-01-02 The Trustees Of Boston College Varied morphology carbon nanotubes and method for their manufacture
US7160532B2 (en) * 2003-03-19 2007-01-09 Tsinghua University Carbon nanotube array and method for forming same
US7160531B1 (en) * 2001-05-08 2007-01-09 University Of Kentucky Research Foundation Process for the continuous production of aligned carbon nanotubes
US20070009421A1 (en) * 2004-12-01 2007-01-11 William Marsh Rice University Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip
US20070020167A1 (en) * 2004-06-22 2007-01-25 Han In-Taek Method of preparing catalyst for manufacturing carbon nanotubes
US20070035226A1 (en) * 2002-02-11 2007-02-15 Rensselaer Polytechnic Institute Carbon nanotube hybrid structures
US20070048521A1 (en) * 2005-08-25 2007-03-01 Rudyard Istvan Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers
US20070053824A1 (en) * 2005-08-12 2007-03-08 Samsung Electronics Co., Ltd. Method of forming carbon nanotubes
US20070054105A1 (en) * 2005-09-05 2007-03-08 Hon Hai Precision Industry Co., Ltd. Thermal interface material and method for making same
US20070090489A1 (en) * 2005-10-25 2007-04-26 Hart Anastasios J Shape controlled growth of nanostructured films and objects
US20070092431A1 (en) * 2005-06-28 2007-04-26 Resasco Daniel E Methods for growing and harvesting carbon nanotubes
US20070189953A1 (en) * 2004-01-30 2007-08-16 Centre National De La Recherche Scientifique (Cnrs) Method for obtaining carbon nanotubes on supports and composites comprising same
US20080014431A1 (en) * 2004-01-15 2008-01-17 Nanocomp Technologies, Inc. Systems and methods of synthesis of extended length nanostructures
US20080020193A1 (en) * 2006-07-24 2008-01-24 Jang Bor Z Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes
US20080017845A1 (en) * 2004-05-25 2008-01-24 The Trustees Of The University Of Pennsylvania Nanostructure Assemblies, Methods And Devices Thereof
US20080023396A1 (en) * 2004-05-13 2008-01-31 Hokkaido Technology Licensing Office Co., Ltd. Fine Carbon Dispesion
US7329698B2 (en) * 2001-08-06 2008-02-12 Showa Denko K.K. Conductive curable resin composition and separator for fuel cell
US20080048364A1 (en) * 2004-07-22 2008-02-28 William Marsh Rice University Polymer / Carbon-Nanotube Interpenetrating Networks and Process for Making Same
US7338684B1 (en) * 2004-02-12 2008-03-04 Performance Polymer Solutions, Inc. Vapor grown carbon fiber reinforced composite materials and methods of making and using same
US20080053922A1 (en) * 2006-09-01 2008-03-06 Honsinger Charles P Jr Nanostructured materials comprising support fibers coated with metal containing compounds and methods of using the same
US20080069760A1 (en) * 2004-06-04 2008-03-20 The Trustees Of Columbia University In The City Of New York Methods For Preparing Single -Walled Carbon Nanoturbes
US20080075954A1 (en) * 2006-05-19 2008-03-27 Massachusetts Institute Of Technology Nanostructure-reinforced composite articles and methods
US7354881B2 (en) * 1999-06-02 2008-04-08 The Board Of Regents Of The University Of Oklahoma Method and catalyst for producing single walled carbon nanotubes
US7354988B2 (en) * 2003-08-12 2008-04-08 General Electric Company Electrically conductive compositions and method of manufacture thereof
US20080247939A1 (en) * 2005-08-29 2008-10-09 University Of The Witwatersrand, Johannesburg Process for Producing Carbon Nanotubes
US7473466B1 (en) * 2000-05-10 2009-01-06 University Of Central Florida Research Foundation, Inc. Filamentous carbon particles for cleaning oil spills and method of production
US20090017301A1 (en) * 2005-12-23 2009-01-15 Ssint-Gobain Technical Fabrics Europe Glass fibres and glass fibre structures provided with a coating containing nanoparticles
WO2009008291A1 (fr) * 2007-07-06 2009-01-15 National Institute Of Advanced Industrial Science And Technology Procédé de fabrication d'un film de nanotubes de carbone, appareil de fabrication de film et film de nanotubes de carbone
US7479052B2 (en) * 2005-12-13 2009-01-20 Samsung Sdi Co., Ltd. Method of growing carbon nanotubes and method of manufacturing field emission device using the same
US20090021136A1 (en) * 2005-05-31 2009-01-22 Coll Bernard F Emitting device having electron emitting nanostructures and method of operation
US20090020734A1 (en) * 2007-07-19 2009-01-22 Jang Bor Z Method of producing conducting polymer-transition metal electro-catalyst composition and electrodes for fuel cells
US7488455B2 (en) * 2001-04-04 2009-02-10 Commonwealth Scientific And Industrial Research Organisation Apparatus for the production of carbon nanotubes
US20090047453A1 (en) * 2007-08-13 2009-02-19 Smart Nanomaterials, Llc Nano-enhanced smart panel
US20090047502A1 (en) * 2007-08-13 2009-02-19 Smart Nanomaterials, Llc Nano-enhanced modularly constructed composite panel
US7494639B2 (en) * 2004-12-28 2009-02-24 William Marsh Rice University Purification of carbon nanotubes based on the chemistry of fenton's reagent
US20090068387A1 (en) * 2006-07-31 2009-03-12 Matthew Panzer Composite thermal interface material including aligned nanofiber with low melting temperature binder
US20090068461A1 (en) * 2003-10-16 2009-03-12 The University Of Akron Carbon nanotubes on carbon nanofiber substrate
US20090081383A1 (en) * 2007-09-20 2009-03-26 Lockheed Martin Corporation Carbon Nanotube Infused Composites via Plasma Processing
US20090081441A1 (en) * 2007-09-20 2009-03-26 Lockheed Martin Corporation Fiber Tow Comprising Carbon-Nanotube-Infused Fibers
US7510695B2 (en) * 1997-03-07 2009-03-31 William Marsh Rice University Method for forming a patterned array of fullerene nanotubes
US20090092832A1 (en) * 2005-12-23 2009-04-09 Saint-Gobain Technical Fabrics Europe Glass fibres coated with size containing nanoparticles
US20090099016A1 (en) * 2005-12-19 2009-04-16 Advanced Technology Materials, Inc. Production of carbon nanotubes
US20100000770A1 (en) * 2005-12-19 2010-01-07 University Of Virginia Patent Foundation Conducting Nanotubes or Nanostructures Based Composites, Method of Making Them and Applications
US7656027B2 (en) * 2003-01-24 2010-02-02 Nanoconduction, Inc. In-chip structures and methods for removing heat from integrated circuits
US7666915B2 (en) * 2007-09-24 2010-02-23 Headwaters Technology Innovation, Llc Highly dispersible carbon nanospheres in a polar solvent and methods for making same
US20100059243A1 (en) * 2008-09-09 2010-03-11 Jin-Hong Chang Anti-electromagnetic interference material arrangement
US20100074834A1 (en) * 2008-09-22 2010-03-25 Samsung Electronics Co., Ltd. Apparatus and method for surface-treating carbon fiber by resistive heating
US7687981B2 (en) * 2006-05-05 2010-03-30 Brother International Corporation Method for controlled density growth of carbon nanotubes
US20100081769A1 (en) * 2008-09-26 2010-04-01 E.I.Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
US7700943B2 (en) * 2005-12-14 2010-04-20 Intel Corporation In-situ functionalization of carbon nanotubes
US20100098931A1 (en) * 2008-06-02 2010-04-22 Texas A & M University System Carbon nanotube fiber-reinforced polymer composites having improved fatigue durability and methods for production thereof
US7862795B2 (en) * 2004-11-16 2011-01-04 Hyperion Catalysis International, Inc. Method for preparing single walled carbon nanotubes
US7867468B1 (en) * 2008-02-28 2011-01-11 Carbon Solutions, Inc. Multiscale carbon nanotube-fiber reinforcements for composites
US7871591B2 (en) * 2005-01-11 2011-01-18 Honda Motor Co., Ltd. Methods for growing long carbon single-walled nanotubes
US7880376B2 (en) * 2001-06-14 2011-02-01 Hyperion Catalysis International, Inc. Field emission devices made with laser and/or plasma treated carbon nanotube mats, films or inks
US20110024409A1 (en) * 2009-04-27 2011-02-03 Lockheed Martin Corporation Cnt-based resistive heating for deicing composite structures
US20110024694A1 (en) * 2009-02-17 2011-02-03 Lockheed Martin Corporation Composites comprising carbon nanotubes on fiber
US8148276B2 (en) * 2005-11-28 2012-04-03 University Of Hawaii Three-dimensionally reinforced multifunctional nanocomposites

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3768867B2 (ja) * 2001-12-03 2006-04-19 株式会社リコー カーボンナノチューブの作製方法
JP3972674B2 (ja) * 2002-02-14 2007-09-05 東レ株式会社 炭素繊維その製造方法および炭素繊維強化樹脂組成物
EP2067741B1 (fr) * 2003-07-28 2017-09-06 William Marsh Rice University Composites à base de polymères comprenant des nanotubes de carbone fonctionnalisés avec silanes.
CN100579900C (zh) * 2004-12-13 2010-01-13 日机装株式会社 单壁碳纳米管的制造方法
EP1877255A4 (fr) * 2005-03-10 2011-03-30 Mat & Electrochem Res Corp Procede et dispositif de production de film mince
JP2009535530A (ja) * 2006-05-02 2009-10-01 ロール インコーポレイテッド ナノ補強材を用いた複合材料中に用いられる補強繊維トウの修飾
US8158217B2 (en) * 2007-01-03 2012-04-17 Applied Nanostructured Solutions, Llc CNT-infused fiber and method therefor
CN101049927B (zh) * 2007-04-18 2010-11-10 清华大学 连续化生产碳纳米管的方法及装置

Patent Citations (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304855A (en) * 1963-05-15 1967-02-21 H G Molenaar & Company Proprie Extractor means for extracting liquid from a liquids containing mass
US4566969A (en) * 1981-09-29 1986-01-28 Crane & Co., Inc. Rolling filter apparatus
US5714089A (en) * 1984-10-31 1998-02-03 Igen International, Inc. Luminescent metal chelatte labels and means for detection
US5731147A (en) * 1984-10-31 1998-03-24 Igen International, Inc. Luminescent metal chelate labels and means for detection
US4797378A (en) * 1986-02-18 1989-01-10 Minnesota Mining And Manufacturing Company Internally modified ceramic fiber
US5093155A (en) * 1988-11-29 1992-03-03 Tonen Corporation Process for sizing reinforcing fiber by applying sulfone compounds containing sulfonyl groups and sized reinforcing fibers obtained thereby
US5595750A (en) * 1991-08-09 1997-01-21 E. I. Du Pont De Nemours And Company Antimicrobial particles of silver and barium sulfate or zinc oxide
US6184280B1 (en) * 1995-10-23 2001-02-06 Mitsubishi Materials Corporation Electrically conductive polymer composition
US7510695B2 (en) * 1997-03-07 2009-03-31 William Marsh Rice University Method for forming a patterned array of fullerene nanotubes
US6863942B2 (en) * 1998-06-19 2005-03-08 The Research Foundation Of State University Of New York Free-standing and aligned carbon nanotubes and synthesis thereof
US20030068432A1 (en) * 1998-08-14 2003-04-10 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube devices
US20020035170A1 (en) * 1999-02-12 2002-03-21 Paul Glatkowski Electromagnetic shielding composite comprising nanotubes
US6221154B1 (en) * 1999-02-18 2001-04-24 City University Of Hong Kong Method for growing beta-silicon carbide nanorods, and preparation of patterned field-emitters by chemical vapor depositon (CVD)
US6994907B2 (en) * 1999-06-02 2006-02-07 The Board Of Regents Of The University Of Oklahoma Carbon nanotube product comprising single-walled carbon nanotubes
US7354881B2 (en) * 1999-06-02 2008-04-08 The Board Of Regents Of The University Of Oklahoma Method and catalyst for producing single walled carbon nanotubes
US6361861B2 (en) * 1999-06-14 2002-03-26 Battelle Memorial Institute Carbon nanotubes on a substrate
US6692717B1 (en) * 1999-09-17 2004-02-17 William Marsh Rice University Catalytic growth of single-wall carbon nanotubes from metal particles
US6673392B2 (en) * 2000-03-15 2004-01-06 Samsung Sdi Co., Ltd. Method of vertically aligning carbon nanotubes on substrates at low pressure using thermal chemical vapor deposition with DC bias
US7473466B1 (en) * 2000-05-10 2009-01-06 University Of Central Florida Research Foundation, Inc. Filamentous carbon particles for cleaning oil spills and method of production
US20040026234A1 (en) * 2000-08-23 2004-02-12 Pierre Vanden Brande Method and device for continuous cold plasma deposition of metal coatings
US7018600B2 (en) * 2001-03-21 2006-03-28 Gsi Creos Corporation Expanded carbon fiber product and composite using the same
US6986853B2 (en) * 2001-03-26 2006-01-17 Eikos, Inc. Carbon nanotube fiber-reinforced composite structures for EM and lightning strike protection
US20030024884A1 (en) * 2001-04-02 2003-02-06 Petrik Viktor Ivanovich Method for removing oil, petroleum products and/or chemical, pollutants from liquid and/or gas and/or surface
US7488455B2 (en) * 2001-04-04 2009-02-10 Commonwealth Scientific And Industrial Research Organisation Apparatus for the production of carbon nanotubes
US7160531B1 (en) * 2001-05-08 2007-01-09 University Of Kentucky Research Foundation Process for the continuous production of aligned carbon nanotubes
US7504078B1 (en) * 2001-05-08 2009-03-17 University Of Kentucky Research Foundation Continuous production of aligned carbon nanotubes
US7157068B2 (en) * 2001-05-21 2007-01-02 The Trustees Of Boston College Varied morphology carbon nanotubes and method for their manufacture
US7880376B2 (en) * 2001-06-14 2011-02-01 Hyperion Catalysis International, Inc. Field emission devices made with laser and/or plasma treated carbon nanotube mats, films or inks
US7329698B2 (en) * 2001-08-06 2008-02-12 Showa Denko K.K. Conductive curable resin composition and separator for fuel cell
US20050090176A1 (en) * 2001-08-29 2005-04-28 Dean Kenneth A. Field emission display and methods of forming a field emission display
US6837928B1 (en) * 2001-08-30 2005-01-04 The Board Of Trustees Of The Leland Stanford Junior University Electric field orientation of carbon nanotubes
US6528572B1 (en) * 2001-09-14 2003-03-04 General Electric Company Conductive polymer compositions and methods of manufacture thereof
US7022776B2 (en) * 2001-11-07 2006-04-04 General Electric Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom
US7011760B2 (en) * 2001-12-21 2006-03-14 Battelle Memorial Institute Carbon nanotube-containing structures, methods of making, and processes using same
US6986877B2 (en) * 2002-01-08 2006-01-17 Futaba Corporation Method for preparing nano-carbon fiber and nano-carbon fiber
US20070035226A1 (en) * 2002-02-11 2007-02-15 Rensselaer Polytechnic Institute Carbon nanotube hybrid structures
US20050026778A1 (en) * 2002-02-25 2005-02-03 Axtell Holly C. Multi-functional protective fiber and methods for use
US20040082247A1 (en) * 2002-03-21 2004-04-29 Shahyaan Desai Fibrous micro-composite material
US20040009115A1 (en) * 2002-06-13 2004-01-15 Wee Thye Shen Andrew Selective area growth of aligned carbon nanotubes on a modified catalytic surface
US6852410B2 (en) * 2002-07-01 2005-02-08 Georgia Tech Research Corporation Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same
US20040007955A1 (en) * 2002-07-09 2004-01-15 Zvi Yaniv Nanotriode utilizing carbon nanotubes and fibers
US20040037767A1 (en) * 2002-08-21 2004-02-26 First Nano, Inc. Method and apparatus of carbon nanotube fabrication
US20040079278A1 (en) * 2002-10-28 2004-04-29 Kamins Theodore I. Method of forming three-dimensional nanocrystal array
US20060052509A1 (en) * 2002-11-01 2006-03-09 Mitsubishi Rayon Co., Ltd. Composition containing carbon nanotubes having coating thereof and process for producing them
US7656027B2 (en) * 2003-01-24 2010-02-02 Nanoconduction, Inc. In-chip structures and methods for removing heat from integrated circuits
US20060083674A1 (en) * 2003-02-14 2006-04-20 Shigeo Maruyama Method for forming catalyst metal particles for production of single-walled carbon nanotube
US7160532B2 (en) * 2003-03-19 2007-01-09 Tsinghua University Carbon nanotube array and method for forming same
US20050009694A1 (en) * 2003-06-30 2005-01-13 Watts Daniel J. Catalysts and methods for making same
US7354988B2 (en) * 2003-08-12 2008-04-08 General Electric Company Electrically conductive compositions and method of manufacture thereof
US20090068461A1 (en) * 2003-10-16 2009-03-12 The University Of Akron Carbon nanotubes on carbon nanofiber substrate
US20100099319A1 (en) * 2004-01-15 2010-04-22 Nanocomp Technologies, Inc. Systems and Methods for Synthesis of Extended Length Nanostructures
US20080014431A1 (en) * 2004-01-15 2008-01-17 Nanocomp Technologies, Inc. Systems and methods of synthesis of extended length nanostructures
US20070189953A1 (en) * 2004-01-30 2007-08-16 Centre National De La Recherche Scientifique (Cnrs) Method for obtaining carbon nanotubes on supports and composites comprising same
US7338684B1 (en) * 2004-02-12 2008-03-04 Performance Polymer Solutions, Inc. Vapor grown carbon fiber reinforced composite materials and methods of making and using same
US7927701B2 (en) * 2004-02-12 2011-04-19 Performance Polymer Solutions, Inc. Vapor grown carbon fiber reinforced composite materials and methods of making and using same
US20080023396A1 (en) * 2004-05-13 2008-01-31 Hokkaido Technology Licensing Office Co., Ltd. Fine Carbon Dispesion
US20080017845A1 (en) * 2004-05-25 2008-01-24 The Trustees Of The University Of Pennsylvania Nanostructure Assemblies, Methods And Devices Thereof
US20060067871A1 (en) * 2004-05-26 2006-03-30 Massachusetts Institute Of Technology Methods and devices for growth and/or assembly of nanostructures
US20080069760A1 (en) * 2004-06-04 2008-03-20 The Trustees Of Columbia University In The City Of New York Methods For Preparing Single -Walled Carbon Nanoturbes
US20070020167A1 (en) * 2004-06-22 2007-01-25 Han In-Taek Method of preparing catalyst for manufacturing carbon nanotubes
US20060002844A1 (en) * 2004-07-02 2006-01-05 Kabushiki Kaisha Toshiba Manufacturing methods of catalysts for carbon fiber composition and carbon material compound, manufacturing methods of carbon fiber and catalyst material for fuel cell, and catalyst material for fuel cell
US20080048364A1 (en) * 2004-07-22 2008-02-28 William Marsh Rice University Polymer / Carbon-Nanotube Interpenetrating Networks and Process for Making Same
US20060062944A1 (en) * 2004-09-20 2006-03-23 Gardner Slade H Ballistic fabrics with improved antiballistic properties
US20060083927A1 (en) * 2004-10-15 2006-04-20 Zyvex Corporation Thermal interface incorporating nanotubes
US7862795B2 (en) * 2004-11-16 2011-01-04 Hyperion Catalysis International, Inc. Method for preparing single walled carbon nanotubes
US20070009421A1 (en) * 2004-12-01 2007-01-11 William Marsh Rice University Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip
US7494639B2 (en) * 2004-12-28 2009-02-24 William Marsh Rice University Purification of carbon nanotubes based on the chemistry of fenton's reagent
US7871591B2 (en) * 2005-01-11 2011-01-18 Honda Motor Co., Ltd. Methods for growing long carbon single-walled nanotubes
US20090021136A1 (en) * 2005-05-31 2009-01-22 Coll Bernard F Emitting device having electron emitting nanostructures and method of operation
US20070092431A1 (en) * 2005-06-28 2007-04-26 Resasco Daniel E Methods for growing and harvesting carbon nanotubes
US20070053824A1 (en) * 2005-08-12 2007-03-08 Samsung Electronics Co., Ltd. Method of forming carbon nanotubes
US20070048521A1 (en) * 2005-08-25 2007-03-01 Rudyard Istvan Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers
US20080247939A1 (en) * 2005-08-29 2008-10-09 University Of The Witwatersrand, Johannesburg Process for Producing Carbon Nanotubes
US20070054105A1 (en) * 2005-09-05 2007-03-08 Hon Hai Precision Industry Co., Ltd. Thermal interface material and method for making same
US20070090489A1 (en) * 2005-10-25 2007-04-26 Hart Anastasios J Shape controlled growth of nanostructured films and objects
US8148276B2 (en) * 2005-11-28 2012-04-03 University Of Hawaii Three-dimensionally reinforced multifunctional nanocomposites
US7479052B2 (en) * 2005-12-13 2009-01-20 Samsung Sdi Co., Ltd. Method of growing carbon nanotubes and method of manufacturing field emission device using the same
US7700943B2 (en) * 2005-12-14 2010-04-20 Intel Corporation In-situ functionalization of carbon nanotubes
US20100000770A1 (en) * 2005-12-19 2010-01-07 University Of Virginia Patent Foundation Conducting Nanotubes or Nanostructures Based Composites, Method of Making Them and Applications
US20090099016A1 (en) * 2005-12-19 2009-04-16 Advanced Technology Materials, Inc. Production of carbon nanotubes
US20090017301A1 (en) * 2005-12-23 2009-01-15 Ssint-Gobain Technical Fabrics Europe Glass fibres and glass fibre structures provided with a coating containing nanoparticles
US20090092832A1 (en) * 2005-12-23 2009-04-09 Saint-Gobain Technical Fabrics Europe Glass fibres coated with size containing nanoparticles
US7687981B2 (en) * 2006-05-05 2010-03-30 Brother International Corporation Method for controlled density growth of carbon nanotubes
US20080075954A1 (en) * 2006-05-19 2008-03-27 Massachusetts Institute Of Technology Nanostructure-reinforced composite articles and methods
US20080020193A1 (en) * 2006-07-24 2008-01-24 Jang Bor Z Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes
US20090068387A1 (en) * 2006-07-31 2009-03-12 Matthew Panzer Composite thermal interface material including aligned nanofiber with low melting temperature binder
US20080053922A1 (en) * 2006-09-01 2008-03-06 Honsinger Charles P Jr Nanostructured materials comprising support fibers coated with metal containing compounds and methods of using the same
WO2009008291A1 (fr) * 2007-07-06 2009-01-15 National Institute Of Advanced Industrial Science And Technology Procédé de fabrication d'un film de nanotubes de carbone, appareil de fabrication de film et film de nanotubes de carbone
US20110014446A1 (en) * 2007-07-06 2011-01-20 Takeshi Saito Method for forming carbon nanotube film, film-forming apparatus, and carbon nanotube film
US20090020734A1 (en) * 2007-07-19 2009-01-22 Jang Bor Z Method of producing conducting polymer-transition metal electro-catalyst composition and electrodes for fuel cells
US20090047453A1 (en) * 2007-08-13 2009-02-19 Smart Nanomaterials, Llc Nano-enhanced smart panel
US20090047502A1 (en) * 2007-08-13 2009-02-19 Smart Nanomaterials, Llc Nano-enhanced modularly constructed composite panel
US20090081383A1 (en) * 2007-09-20 2009-03-26 Lockheed Martin Corporation Carbon Nanotube Infused Composites via Plasma Processing
US20090081441A1 (en) * 2007-09-20 2009-03-26 Lockheed Martin Corporation Fiber Tow Comprising Carbon-Nanotube-Infused Fibers
US7666915B2 (en) * 2007-09-24 2010-02-23 Headwaters Technology Innovation, Llc Highly dispersible carbon nanospheres in a polar solvent and methods for making same
US7867468B1 (en) * 2008-02-28 2011-01-11 Carbon Solutions, Inc. Multiscale carbon nanotube-fiber reinforcements for composites
US20100098931A1 (en) * 2008-06-02 2010-04-22 Texas A & M University System Carbon nanotube fiber-reinforced polymer composites having improved fatigue durability and methods for production thereof
US20100059243A1 (en) * 2008-09-09 2010-03-11 Jin-Hong Chang Anti-electromagnetic interference material arrangement
US20100074834A1 (en) * 2008-09-22 2010-03-25 Samsung Electronics Co., Ltd. Apparatus and method for surface-treating carbon fiber by resistive heating
US20100081769A1 (en) * 2008-09-26 2010-04-01 E.I.Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
US20110024694A1 (en) * 2009-02-17 2011-02-03 Lockheed Martin Corporation Composites comprising carbon nanotubes on fiber
US20110024409A1 (en) * 2009-04-27 2011-02-03 Lockheed Martin Corporation Cnt-based resistive heating for deicing composite structures

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9573812B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US9574300B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US8580342B2 (en) 2009-02-27 2013-11-12 Applied Nanostructured Solutions, Llc Low temperature CNT growth using gas-preheat method
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
US9260646B2 (en) 2012-05-09 2016-02-16 Laird Technologies, Inc. Polymer matrices functionalized with carbon-containing species for enhanced thermal conductivity
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
US10533247B2 (en) * 2012-12-29 2020-01-14 Tsinghua University Method for growing carbon nanotubes
US20140186547A1 (en) * 2012-12-29 2014-07-03 Hon Hai Precision Industry Co., Ltd. Reactor and method for growing carbon nanotube using the same
US9567218B2 (en) * 2012-12-29 2017-02-14 Tsinghua University Reactor and method for growing carbon nanotube using the same
US20170057824A1 (en) * 2012-12-29 2017-03-02 Tsinghua University Method for growing carbon nanotubes
US9987608B2 (en) 2014-09-19 2018-06-05 NanoSynthesis Plus, Ltd. Methods and apparatuses for producing dispersed nanostructures
US10099930B2 (en) 2014-12-05 2018-10-16 Q-Flo Limited Method for the production of carbon nanotube structures
WO2016087857A1 (fr) * 2014-12-05 2016-06-09 Q-Flo Limited Procédé
CN105908491A (zh) * 2016-05-31 2016-08-31 哈尔滨工业大学 制备表面生长有碳纳米管的连续碳纤维的装置和方法
WO2018034625A1 (fr) * 2016-08-16 2018-02-22 Istanbul Teknik Universitesi Nanotubes de carbone à répartition aléatoire et/ou croissance verticale/horizontale sur des nanofibres polymères et leurs composites
US20210187788A1 (en) * 2018-05-31 2021-06-24 Lintec Corporation Method of producing carbon-resin composite material, and composite structure for producing carbon-resin composite material
EP3810547A4 (fr) * 2018-06-22 2022-04-06 The Government of the United States of America, as represented by the Secretary of the Navy Appareil et procédé de croissance de structures de carbone sp2 cylindriques ultralongues distinctes
WO2020071655A1 (fr) * 2018-10-04 2020-04-09 Awexomeray Procédé de préparation d'un fil comprenant des nanotubes de carbone et fil ainsi préparé
US11408097B2 (en) 2018-10-04 2022-08-09 Awexome Ray, Inc. Process for preparing a yarn comprising carbon nanotubes and yarn prepared thereby
US11453591B2 (en) 2018-11-30 2022-09-27 Awexome Ray, Inc. Process for preparing a carbon nanotube sheet comprising a uniaxially aligned yarn and carbon nanotube sheet prepared thereby
US11600462B2 (en) 2019-01-24 2023-03-07 Awexome Ray, Inc. Emitter with excellent structural stability and enhanced efficiency of electron emission and X-ray tube comprising the same
US11798773B2 (en) 2019-01-24 2023-10-24 Awexome Ray, Inc. Emitter with excellent structural stability and enhanced efficiency of electron emission and X-ray tube comprising the same
US10643816B1 (en) 2019-04-04 2020-05-05 aweXomeRay Co., Ltd. X-ray emitting device comprising a focusing electrode composed of a ceramic-based material
US11195684B2 (en) 2019-07-26 2021-12-07 Awexome Ray, Inc. Field emission apparatus with superior structural stability and X-ray tube comprising the same

Also Published As

Publication number Publication date
JP5604506B2 (ja) 2014-10-08
EP2417288A4 (fr) 2013-10-30
CN102388172A (zh) 2012-03-21
KR20120002980A (ko) 2012-01-09
WO2010118381A1 (fr) 2010-10-14
AU2010233113A1 (en) 2011-10-13
CN102388172B (zh) 2015-02-11
JP2012523368A (ja) 2012-10-04
BRPI1014162A2 (pt) 2016-04-26
CA2757474A1 (fr) 2010-10-14
EP2417288A1 (fr) 2012-02-15
ZA201106734B (en) 2012-08-28

Similar Documents

Publication Publication Date Title
US20100260931A1 (en) Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber
US8580342B2 (en) Low temperature CNT growth using gas-preheat method
US20200010983A1 (en) Apparatuses and Methods for Large-Scale Production of Hybrid Fibers Containing Carbon Nanostructures and Related Materials
US9573812B2 (en) CNT-infused metal fiber materials and process therefor
JP5823393B2 (ja) 複合繊維へのナノ粒子の組み込み
US9447259B2 (en) Composite materials formed by shear mixing of carbon nanostructures and related methods
AU2012326007B2 (en) Systems and methods for continuously producing carbon nanostructures on reusable substrates
US20110171469A1 (en) Cnt-infused aramid fiber materials and process therefor
US20110168083A1 (en) Cnt-infused ceramic fiber materials and process therefor
JP2013500937A5 (fr)
AU2010217757A1 (en) CNT-infused glass fiber materials and process therefor

Legal Events

Date Code Title Description
AS Assignment

Owner name: APPLIED NANOSTRUCTURED SOLUTIONS, LLC, MARYLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LOCKHEED MARTIN CORPORATION;REEL/FRAME:024349/0133

Effective date: 20100429

AS Assignment

Owner name: LOCKHEED MARTIN CORPORATION, MARYLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MALECKI, HARRY C.;SHAH, TUSHAR K.;ALBERDING, MARK R.;SIGNING DATES FROM 20100524 TO 20100525;REEL/FRAME:024591/0337

AS Assignment

Owner name: APPLIED NANOSTRUCTURED SOLUTIONS, LLC, MARYLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LOCKHEED MARTIN CORPORATION;REEL/FRAME:025913/0473

Effective date: 20110302

AS Assignment

Owner name: APPLIED NANOSTRUCTURED SOLUTIONS, LLC, MARYLAND

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE ERRONEOUSLY LISTED SERIAL NO. 12/757,901 PREVIOUSLY RECORDED ON REEL 025913 FRAME 0473. ASSIGNOR(S) HEREBY CONFIRMS THE SERIAL NO. 12/757,901 SHOULD BE REMOVED FROM THE ASSIGNMENT.;ASSIGNOR:LOCKHEED MARTIN CORPORATION;REEL/FRAME:028720/0565

Effective date: 20110302

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE